JPH06157013A - Stabilized red phosphorus composition and flame retardant polymeric material - Google Patents

Abstract

PURPOSE:To provide a stabilized red phosphorus composition nearly completely suppressing the smell of a phosphine and a flame retardant polymeric material containing the composition blended therein. CONSTITUTION:This stabilized red phosphorus composition is obtained by blending coated modified red phosphorus coated with an inorganic and/or an organic compound with zeolite (in an amount of 1-20 pts.wt. based on 100 pts.wt. coated modified red phosphorus). This flame retardant polymeric material is prepared by blending 100 pts.wt. combustible thermosetting resin or thermoplastic resin with the stabilized red phosphorus composition in an amount within the range of 0.5-50 pts.wt. expressed in terms of P.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a stabilized red phosphorus composition and a flame-retardant polymer material containing the same, more specifically, inorganic or / and organic coated modified red phosphorus containing zeolite as a phosphine catcher. The present invention relates to a stabilized red phosphorus composition obtained by the method and a flame-retardant polymer material comprising the polymer composition containing the red phosphorus composition as a flame retardant.

[0002]

2. Description of the Related Art It has been well known that red phosphorus is compounded in a polymer material represented by a synthetic resin to exert an excellent flame retardant effect, and it is actually used as a flame retardant. However, if red phosphorus is used as it is, it causes a hydrolysis reaction with water to generate harmful phosphine gas.Therefore, many modified red phosphorus coated with various organic or inorganic materials are used for the purpose of preventing this. Proposed.
For example, modified red phosphorus obtained by coating red phosphorus with a thermosetting resin (JP-A-51-105996), modified red phosphorus obtained by converting the surface of red phosphorus to a metal phosphide and then coating with a thermosetting resin (special JP-A-52-125489), modified red phosphorus coated with a metal oxide (JP-A-52-131695), modified red phosphorus double-coated with a metal oxide and a thermosetting resin (JP-A-52-131695). JP-A-61-111342 and JP-A-62-21704), modified red phosphorus obtained by coating red phosphorus in triple layers with aluminum hydroxide and other metal hydroxides and an inorganic or organic coating agent (JP Examples of this include modified red phosphorus in which the surface of red phosphorus particles is coated with an electroless plating film (JP-A-63-69704).

However, it is difficult to effectively suppress the generation of phosphine gas by the coating treatment with these modified red phosphorus according to the prior art, and a sufficiently stabilized one has not been developed yet. Since phosphine gas is accompanied by an unpleasant odor even in a very small amount, its use is significantly restricted from the viewpoint of working environment, despite the fact that red phosphorus has an excellent flame retardant effect. It is the current situation.

[0004]

Considering the aspect in which phosphine gas is generated when the modified red phosphorus coated with coating is used as a flame retardant, the following two situations can be pointed out. One of them is that when the modified red phosphorus is hermetically packaged, stored and transported for a long period of time, and then opened, it hydrolyzes with time even at room temperature to generate an unpleasant phosphine odor. Another cause of gas generation is that the processing and molding temperature of the thermoplastic resin is 200 ° C. or higher in order to improve workability when manufacturing the flame-retardant resin using the modified red phosphorus.
At times, the temperature range may exceed 300 ° C,
This is because the stability of the coating film at such a high temperature is insufficient.

In view of the above situation, the present inventor has been earnestly researching a stabilizing means capable of sufficiently suppressing the generation of phosphine gas accompanying the decomposition of red phosphorus. Then, it was confirmed that the odor of phosphine was extremely effectively suppressed, and that the compound containing this in a polymer material such as a synthetic resin exhibited excellent flame retardancy.

The present invention was developed based on the above findings, and its object is to provide a stabilized red phosphorus composition in which generation of phosphine odor is almost completely suppressed, and a flame-retardant polymer material containing the same. To provide.

[0007]

The stabilized red phosphorus composition according to the present invention for attaining the above object is characterized in that the coated modified red phosphorus is mixed with zeolite.

The coating-modified red phosphorus used in the present invention is obtained by coating the surface of red phosphorus particles with an inorganic or / and organic compound to impart hydrolysis resistance. The red phosphorus particles to be subjected to the coating treatment are not restricted by the production history thereof, but it is desirable that the red phosphorus itself is hydrolysis resistant and inactive. From this meaning, it is not preferable to use fine red phosphorus particles having a large specific surface area.
It is recommended to remove as much as possible particles having a particle size of less than 1 μm. However, from a practical point of view, it is preferably 100 μm or less, and the average particle size is 5 to 30 μm, preferably 10 to 2
A range of 0 μm is preferred. These red phosphorus powders can be prepared by crushing a red phosphorus ingot, but it is preferable to use substantially red spherical phosphorus particles from the production stage.

The inorganic coating film coated on the surface of the red phosphorus particles includes fine metal oxide type and metal type. this house,
Metal oxides include metal hydroxides such as hydrous oxides and hydrated oxides, and in particular Mg, Zn, Co, Cu, Al, T
One or more oxides selected from i, Zr or Si are preferably used for the purpose of the present invention. A known method is used for coating the red phosphorus particles with these metal oxides, and the coating amount thereof is 3 to 30% by weight, preferably 5 to 20% as the metal oxide (converted to an anhydride) with respect to red phosphorus.
It is in the range of% by weight.

Further, examples of the metal-based coating include an electroless plating layer and a metal phosphide layer. Ni is preferable as the metal for electroless plating, but Ni, Co, Zn,
It may be an alloy such as Cu. In many cases, the coating amount is set in the range of 0.5 to 50% by weight, preferably 2 to 40% by weight, based on the total amount of the red phosphorus coating.

The modified red phosphorus coated with an organic compound is one coated with a thermosetting resin or one coated with a resin by radical polymerization, and the coating means for the red phosphorus particles is performed by a known method. Examples of the thermosetting resin include phenol resin, urea resin, melamine resin, furfuryl alcohol resin, epoxy resin, and fluorine-containing or silicon-containing thermosetting resin. It is preferable to employ a coating method in which the prepared one is used to polymerize in an aqueous slurry of red phosphorus. The coating amount of the thermosetting resin is not particularly limited, but is generally 1 to 30 with respect to red phosphorus.
The range is preferably wt%, preferably 2 to 20 wt%.

Examples of the monomer that can be used for resin coating by radical polymerization include methacrylic acid esters such as methyl methacrylate and ethyl methacrylate, acrylic acid esters such as methyl acrylate and ethyl acrylate, and methacrylic acid. One or more selected from acrylic acid, styrene, vinyl acetate, acrylonitrile and the like can be mentioned. The amount of these monomers used is usually 3 to 80% by weight with respect to red phosphorus,
It is preferably in the range of 20 to 60% by weight. As coating conditions, a red phosphorus slurry having a pH of 2 to 6 and a polymerization initiator of a peroxide type, an azobis compound type, or a sulfite compound type in the presence of a crosslinking agent, if necessary, in an inert gas atmosphere at 30 to It is preferable to polymerize while heating in the temperature range of 90 ° C.

Further, it is often preferred as a modified red phosphorus that the above-mentioned inorganic and organic coatings are formed as a double layer. For example, a composite coating such as a composition in which a thermosetting resin coating is applied on a metal oxide coating layer, a composition in which titanium oxide is coated on a metal plating film, or a resin coating composition by titanium oxide and radical polymerization is applicable. . In particular, composite coating using titanium oxide makes it possible to obtain white modified red phosphorus by hiding the dark red color, which is an essential attribute of red phosphorus, and the metallic color of the plating film.

Zeolite is blended with the above-mentioned coated modified stabilized red phosphorus. This zeolite may be either synthetic or natural, but is preferably a synthetic zeolite in terms of quality and adsorption function. Particularly, a synthetic zeolite having a composition represented by the following general formula is preferably used. _{xM 2 / n O · Al 2} O 3 · ySiO 2 · zH 2 O wherein, M is a monovalent or divalent metal ions NH ^4+, n is the valence of M, x, y and z are each 0.8 ≦ x ≦ 1.2
, 1.8 ≤ y ≤ 20, and 0 ≤ z ≤ 20].

Examples of this type of zeolite include zeolite A, zeolite X, zeolite Y, zeolite L, analsite, mordenite, ZSM-5, ZSM.
-11, clinoptilolite and the like,
These are used as one kind or as a mixture of two or more kinds. The exchangeable cation of these zeolites is not particularly limited, but when M is a monovalent metal ion in the above general formula, it is Na ⁺ , K ⁺ , NH ₄ ⁺ , Li ⁺ , Ag ^+, etc. Ca ²⁺ , Mg ²⁺ , S for metal ions
Typical examples are r ²⁺ , Zn ²⁺ , Co ²⁺ , Cu ²⁺ and Mn ²⁺ .

Generally, since red phosphorus particles are more easily hydrolyzed on the alkaline side, these zeolites are those in which free alkali is removed as much as possible, and the equilibrium pH is at least 1.
It must be 0.0 or less. This equilibrium p
H is the supernatant pH after 10 g of zeolite is dispersed in 100 ml of pure water and stirred for 1 hour at room temperature. The zeolite preferably has an average particle size at least smaller than that of red phosphorus, and it is desirable to select and use one having a range of 0.5 to 10 μm.

The zeolite compounded in the coated modified red phosphorus in the present invention mainly functions as a phosphine catcher. In addition to this, it imparts an additional function such as improvement of the heat stability of the resin and imparting of antibacterial property. In order to achieve this, the amount of sodium in the zeolite should be 10% by weight or less as Na ₂ O C
It is preferable to use a, Zn, Cu, or Ag substitution type zeolite A or zeolite X.

The blending amount of zeolite with respect to the modified red phosphorus varies depending on the purpose of use, the mode of use, the type of the coated modified red phosphorus or the physical properties of the zeolite, etc. It is set in the range of 1 to 20 parts by weight, preferably 2 to 10 parts by weight. If the content of zeolite is less than 1 part by weight, the function of preventing odor of phosphine will be incomplete, and addition in excess of 20 parts by weight will not contribute to improving the effect.

These stabilized red phosphorus compositions may contain metal hydroxides such as Mg, Al and Zr, other inorganic flame retardants such as antimony oxide, various phosphoric acid esters, and phosphorus phosphite, depending on the mode of use. An organic flame retardant such as an acid ester and a diluent such as titanium oxide, aluminum oxide, silica, silicate or carbon black can be used in combination. In particular, the combined use with a metal hydroxide compound and / or carbon black can impart excellent flame retardancy to a polymer material.

The flame-retardant polymeric material according to the present invention containing the above-mentioned stabilized red phosphorus composition is compounded in an amount of 0.5 to 50 parts by weight with P of the stabilized red phosphorus composition based on 100 parts by weight of the polymeric material. What is done is a structural feature.

When the content of the stabilized red phosphorus composition is less than 0.5 parts by weight as P, the effect of imparting flame retardancy decreases, and
If it exceeds the weight part, it becomes difficult to mix it with the polymer material. A more preferable compounding amount is in the range of 1 to 10 parts by weight as P per 100 parts by weight of the polymer material, and in the case of a high concentration compounding exceeding 10% by weight, a so-called one-pack type containing other auxiliary additives is also added. The masterbatch is convenient for later use. Usually, as other auxiliary additives that can be blended,
Plasticizer, solvent, stabilizer, filler, colorant, antioxidant,
Examples include UV inhibitors.

The polymer material to which flame retardancy is imparted is not limited as long as it is a polymer substance, and various synthetic resins, rubbers, wood, etc. are applied. Among them, the synthetic resins are flammable synthetic resins which are required to be flame-retardant at the time of use, and the types of thermosetting resin and thermoplastic resin are not limited. Examples of the thermosetting resin include phenol resin, urea resin, melamine resin, unsaturated polyester resin, epoxy resin, silicon resin, diacrylic phthalate resin, polyurethane resin and the like. On the other hand, as the thermoplastic resin, polyethylene, poly α-olefins such as polypropylene, copolymers with other monomers containing at least α-olefin, polystyrene, methacrylic resin, styrene-acrylonitrile copolymer (AS resin ),
Acrylonitrile-butadiene-styrene resin (ABS resin), polyvinyl chloride, fluororesin, polyamide, polyimide, polycarbonate, polyacetal, thermoplastic polyester, cellulose acetate (cellulose resin), polysulfone thermoplastic polyimide, polyphenylene oxide, polybutylene ionomer Resin etc. can be illustrated. The forms of these synthetic resins are various molding materials, paints, adhesives, etc., and are not particularly limited.

As the rubbers, combustible rubbers which are required to be flame-retardant at the time of use are targeted. For example, SBR, B
R, IR, EPM, EPDM, NBR, CR, IIR,
Examples thereof include urethane rubber, silicone rubber, fluorinated rubber, and synthetic rubber such as thermoplastic elastomer. Further, the wood may be applied to flame-retardant plywood, but the modified red phosphorus is mainly used for adhesives. That is, a disaster-preventing and flame-retardant plywood can be obtained by using an adhesive containing modified red phosphorus in the production of the laminated plywood. In addition, a flame-retardant coating film can be formed on wood by incorporating it in a paint for wood applications.

[0024]

[Function] Modified red phosphorus in which an inorganic or organic coating layer is formed to stabilize the red phosphorus powder is significantly improved in hydrolysis resistance and stabilized as compared with untreated red phosphorus powder before coating. . However, since the phosphine odor gives a strong unpleasant sensation even if it is an extremely small amount, it is difficult to sufficiently suppress the unpleasant odor only by the above coating treatment. In particular, this unpleasant odor is generated at the time of opening the packaging or container, kneading into the resin, molding, and the like, and therefore it is not safe even if the phosphine odor is prevented after the coating treatment.

According to the stabilized red phosphorus composition of the present invention, the phosphine odor generation is extremely effectively suppressed not only at room temperature but also under heating by adding zeolite to the above-mentioned coated modified red phosphorus. It It was previously known that certain kinds of specific zeolites adsorb phosphine, but modified red phosphorus mixed with them, regardless of the type of zeolite, has the effect of suppressing the phosphine odor over a long period of time. What to do is totally unexpected. That is, according to the stabilized red phosphorus composition of the present invention, the inorganic or / and organic inert coating applied to the surface of the red phosphorus particles effectively functions to suppress the hydrolysis of red phosphorus. As a result of the gas adsorption capacity of the compounded zeolite acting synergistically as a phosphine catcher, the generation of phosphine gas is almost completely prevented. The action of the zeolite as a phosphine catcher is excellent in the zeolite obtained by substituting sodium metal with other metal ions by ion exchange, and can also impart other preferable additional functions.

Further, since the flame-retardant polymer material according to the present invention contains the above-mentioned stabilized red phosphorus composition, the original flame-retardant effect of red phosphorus can be obtained without generating phosphine gas. I own it.

[0027]

EXAMPLES The coated modified red phosphorus and zeolite used as samples in the following Examples and Comparative Examples are as follows. Coated modified red phosphorus; P-1: Titanium-aluminum double metal hydroxide as an oxide in red phosphorus powder having an average particle size of 17 μm 1
Coated in an amount of 1.5% by weight. P-2: Spherical red phosphorus powder having an average particle diameter of 24.5 μm, coated with a titanium-aluminum-based mixed metal oxide as an oxide in an amount of 10.3% by weight. P-3: Spherical red phosphorus powder having an average particle diameter of 24.5 μm formed by a nickel plating film containing 8% by weight of Ni by electroless plating. P-4: 40% by weight to the same coated modified red phosphorus as sample P-3
Titanium dioxide and cross-linked polymerized methyl methacrylate resin coated. P-5: The same modified red phosphorus as sample P-1 coated with phenol resin.

Zeolite; Z-1: Na ₂ O _(0.1) ZnO _(0.9)・ Al ₂ O ₃・ 2.5 SiO ₂・ 4.5 H
₂ O, crystalline form (X-ray diffraction) type A, average particle size 2.6 μm,
Equilibrium pH 9.0 Z-2: Na ₂ O _(0.1) CuO _(0.9)・ Al ₂ O ₃・ 2.5 SiO ₂・ 4.5 H
₂ O, crystalline form (X-ray diffraction) type A, average particle size 2.5 μm,
Equilibrium pH 9.0 Z-3: Na ₂ O _(0.1) Ag ₂ O _(0.2) ZnO _(0.7)・ Al ₂ O ₃・ 2.5 S
iO ₂ · 4.0 H ₂ O, crystalline form (X-ray diffraction) type A, average particle size 1.2 μm, equilibrium pH 9.0 Z-4: Na ₂ O _(0.2) CuO _(0.8) · Al ₂ O ₃ · 2.8 SiO ₂ / 3H
₂ O, crystal form (X-ray diffraction) X type, average particle size 2.8 μm, equilibrium pH 9.0 Z-5: Na ₂ O _(0.2) CuO ( _(0.8)・ Al ₂ O ₃・ 10 SiO ₂ , crystal Form (X-ray diffraction) mordenite, average particle size 4.5 μm, equilibrium pH 7.5

Further, the amount of phosphine gas generated was measured by enclosing 0.5 g of the sample in a hermetically sealed container which had been replaced with an N ₂ gas atmosphere, holding it at a predetermined temperature for a predetermined time, and then sampling the gas in the container to detect phosphine gas. The gas detection measurement method was used to evaluate the phosphine (PH ₃ ) concentration using a tube [Gastech detector tube: detection concentration 0.15 ppm, manufactured by Kitazawa Sangyo Co., Ltd.].

Examples 1 to 5 and Comparative Example 1 Stabilized red phosphorus compositions were prepared by mixing 8 parts by weight of various zeolites with 100 parts by weight of the stabilized modified red phosphorus of Sample P-1. For each composition obtained, the amount of hongfin gas generated was measured at room temperature and at a temperature of 250 ° C. The obtained results are shown in Table 1. For comparison, the amount of phosphine gas generated was also measured for the coated modified red phosphorus containing no zeolite, and the results are also shown in Table 1 (Comparative Example 1).
From the results of Table 1, the stabilized red phosphorus compositions of the present invention according to Examples 1 to 5 in which zeolite is added, the generation amount of phosphine gas is obviously suppressed as compared with Comparative Example 1 in which zeolite is not added. Was recognized.

[0031]

[Table 1]

Examples 6 to 11 and Comparative Examples 2 to 6 To 100 parts by weight of each coated modified red phosphorus shown in Table 2, Cu-substituted zeolite of Sample Z-4 was blended at a ratio shown in Table 2 for stabilization. A red phosphorus composition was prepared. Room temperature (3
The phosphine gas generation amount was measured at 0 days) and heating (250 ° C., 1 hour), and the results are shown in Table 2 in comparison. Comparative Examples 2 to 6 are the results when the corresponding zeolite was not added.

[0033]

[Table 2]

Examples 12 to 18 The stabilized red phosphorus compositions obtained in the above examples were mixed with the following ingredients and poured into a mold (12.7 mm x 12.7 mm x 127 mm), and the mixture was heated at 100 ° C for 6 hours. An epoxy resin molding was prepared by heating and curing. No odor of phosphine was generated in the process of producing this test piece, and the generation amount was not detected when measured by the above method. Epoxy resin 100 parts by weight ["Epicoat 828" manufactured by Yuka Shell Epoxy Co., Ltd.] Anhydrous curing agent 80 parts by weight ["Hardener" manufactured by Ciba-Geigy Co., Ltd.] Aluminum hydroxide 100 parts by weight ["Hijilite H32-I""Showa Light Metal Co., Ltd.] 6 parts by weight of stabilized red phosphorus composition P

With respect to the epoxy resin molding thus prepared, the amount of phosphine gas generated and the flame resistance were evaluated, and the results are shown in Table 3. The flame resistance was evaluated by the following measuring method. Measurement of flame resistance: Measured by the flame resistance test A method of JIS K-6911. The epoxy resin molding (blank) containing no stabilized red phosphorus composition was flammable.

[0036]

[Table 3]

Examples 19 to 22 55 parts by weight based on 100 parts by weight of a resin composition prepared by mixing 100 parts by weight of an unsaturated polyester with the stabilized red phosphorus composition of Examples 2 and 4 and a flame retardant at a ratio shown in Table 4. 1 part by weight of methyl ethyl ketone peroxide (curing catalyst) and an appropriate amount of cobalt naphthenate are mixed and uniformly mixed, poured into a mold (12.7 mm × 12.7 mm × 127 mm), and heat-cured at 100 ° C for 2 hours to polyester. A resin molded body was prepared.
No phosphine odor was generated during the production of this test piece, and no phosphine gas was detected by the measurement using the gas detector tube. About the obtained test piece, Example 12
A flame resistance test was conducted using the same measurement method as in Table 4, and the results are shown in Table 4.
It was shown to.

[0038]

[Table 4]

Examples 23 to 29 Various thermoplastic resin compositions were prepared according to the formulations shown in Table 5, and heated at 180 to 270 ° C. to form 1 roll with two rolls.
After kneading for 0 minutes, test piece (12.7mm x 3mm x 12.7mm)
Was produced. No phosphine odor was generated in the process of producing this test piece, and no phosphine gas was detected by the measurement using the gas detector tube. The test piece thus obtained was tested for flame resistance. The flame resistance in this case is UL-94.
The burning test was conducted, and V-2 or higher was passed. The results are shown in Table 5.

[0040]

[Table 6]

[0041]

As described above, according to the present invention, the generation of toxic and malodorous phosphine gas is almost completely suppressed by incorporating zeolite into the modified red phosphorus powder coated with an inorganic substance and / or an organic substance. A stabilized red phosphorus composition can be provided. In addition, the stabilized red phosphorus composition described above can be imparted to the synthetic resin as it is, which is the inherent flame retardancy of red phosphorus. Therefore, it must be supplied as an excellent flame-retardant polymer material. Is possible. In particular, since it is possible to impart flame retardancy to a thermoplastic resin having a high processing temperature in a good working environment, its industrial significance is extremely large.

Claims (5)

[Claims] 1. A stabilized red phosphorus composition, characterized in that a coated modified red phosphorus is mixed with zeolite. 2. The coated modified red phosphorus is Mg, Zn, Co,
The red phosphorus particles are coated with one or more metal oxides selected from Cu, Al, Ti, Zr or Si or / and a thermosetting resin.
A stabilized red phosphorus composition as described. 3. The stabilized red phosphorus composition according to claim 1, wherein the zeolite has a composition represented by the following general formula. xM _{2 / n} O · Al ₂ O ₃ · ySiO ₂ · zH ₂ O [In the formula, M is a monovalent or divalent metal ion, NH ₄ ⁺ ,
n is the valence of M, and x, y and z are 0.8 ≦ x ≦, respectively.
1.2, 1.8 ≦ y ≦ 20, 0 ≦ z ≦ 20] 4. The stabilized red phosphorus composition according to claim 1, 2 or 3, which comprises 1 to 20 parts by weight of zeolite with respect to 100 parts by weight of the coated modified red phosphorus. 5. The polymer material according to claim 1,
A flame-retardant polymer material comprising the stabilized red phosphorus composition described in 2, 3, or 4 as P in an amount of 0.5 to 50 parts by weight.